Multifunctional protective coatings and their manufacturing methods, and products with coatings.

Abstract

The invention relates to a multifunctional protective coating, a method of fabrication, a coating product, and its application. The multifunctional protective coating contains a material with the chemical formula SixNy, which satisfies the following characteristics: (a) x and y are atomic ratios, with 0.39 ≤ x ≤ 0.43 and 0.57 ≤ y ≤ 0.61; (b) the full width at half maximum (FWHM) of the Fourier transform infrared (FTIR) spectrum at the peak in the range 838–875 cm⁻¹ is 247–313 cm⁻¹; (c) the refractive index at a wavelength of 550 nm is 2.0–2.2; and (d) the hydrogen content, expressed as a percentage of atoms, is ≤ 1%. This multifunctional protective coating combines high refractive index, high nanohardness, high scratch resistance, low stress, and high durability.

Description

Multifunctional protective coating, preparation method thereof, coated product and application thereof

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to Chinese patent application number 2023110205384 filed with the China Patent Office on August 14, 2023, entitled “Multifunctional protective coating, preparation method thereof, coated product and application thereof”, the entire contents of which are incorporated by reference into this application. Technical Field

[0003] The present application relates to the field of coating protection technology, and in particular to a multifunctional protective coating, a preparation method thereof, and a coated product and its application. Background Art

[0004] 3C products, also known as "information appliances," are a collective term for computer, communication, and consumer electronics products, such as computers, tablets, mobile phones, and digital audio players. Because 3C products are generally small, the word "small" is often added to the middle of the name, making them commonly referred to as "3C small appliances."

[0005] Among the hardware materials used in 3C products, such as cover panels, glass and plastic have gradually become the primary raw materials for these products due to their lower cost and lighter weight. Due to their low hardness, brittleness, and transparency, a wide variety of protective coatings have been developed for these surfaces. With technological advancements, the technological content of 3C products has gradually increased, and protective coatings on glass and plastic surfaces are increasingly demanding, specifically requiring high refractive index, high scratch resistance, high hardness, and high durability. Existing research focuses primarily on a single characteristic of SiN coatings. For example, existing published research often focuses on the refractive index parameter of SiN coatings, while ignoring properties such as hardness, scratch resistance, stress, and durability. Existing research on SiN coatings that simultaneously possess multifunctional requirements—specifically, high hardness, high refractive index, high scratch resistance, low stress, and durability—is largely unresolved. However, with the technological advancement of 3C products, the demand for multifunctional, high-standard protective coatings will inevitably emerge in the future.

[0006] Therefore, it is of great significance to develop a multifunctional protective coating that has high refractive index, high scratch resistance, high hardness, low stress and high durability.

[0007] Application Contents

[0008] One object of the present application is to provide a multifunctional protective coating having high refractive index, high scratch resistance, high nanohardness, low stress and high durability.

[0009] Another object of the present application is to provide a method for preparing a multifunctional protective coating.

[0010] Another object of the present application is to provide an application of a multifunctional protective coating in a coated product.

[0011] Another object of the present application is to provide a coated product comprising a multifunctional protective coating.

[0012] In order to achieve the above-mentioned purpose of the present application, the present application provides a multifunctional protective coating having a chemical formula of Si x N y The material satisfies the following characteristics:

[0013] (a) x and y are atomic ratios, and 0.39≤x≤0.43, 0.57≤y≤0.61;

[0014] (b) Fourier transform infrared spectrum with peak positions ranging from 838 to 875 cm -1 The half-wave peak width at the -1 ;

[0015] (c) The refractive index at 550 nm is 2.0 to 2.2;

[0016] (d) The hydrogen content, calculated by atomic number, is ≤ 1%.

[0017] In some embodiments, the refractive index at 550 nm is 2.04-2.13.

[0018] In some embodiments, the nanohardness of the coating ranges from 25 to 30 GPa.

[0019] In some embodiments, the coating has a thickness of 0.01 to 6.0 μm.

[0020] Another aspect of the present application provides a method for preparing a multifunctional protective coating, comprising the following steps:

[0021] The constituent elements of the multifunctional protective coating are deposited on at least a portion of the surface of the substrate in a preset proportion by physical vapor deposition to form the multifunctional protective coating.

[0022] In some embodiments, the physical vapor deposition method is at least one of vacuum evaporation, sputtering, arc plasma plating, ion plating and molecular beam epitaxy.

[0023] In some embodiments, the sputtering coating is magnetron sputtering coating, and optionally, is radio frequency magnetron sputtering coating, direct current magnetron sputtering coating, or radio frequency assisted direct current magnetron sputtering coating.

[0024] In some embodiments, the multifunctional protective coating is formed by sputtering and depositing on at least a portion of the surface of the substrate using a silicon target under the condition of introducing a mixed gas of argon and nitrogen-containing gas.

[0025] In some embodiments, the nitrogen-containing gas is nitrogen, and the gas volume ratio of the argon gas to the nitrogen gas is (0.61-0.71):1.

[0026] In some embodiments, the preparation method includes at least one of the following features:

[0027] The temperature of sputtering deposition is 30-330°C;

[0028] The total pressure of the mixed gas is 0.05-1.2 Pa;

[0029] The nitrogen gas has a gas flow rate of 56 to 300 sccm;

[0030] The power density of the silicon target is 1.5 to 2.4 W / cm 2 ;

[0031] The bias voltage of the substrate is -180 to -20 V;

[0032] The sputtering deposition time is 10 to 300 minutes;

[0033] The background vacuum degree of the vacuum chamber used for sputtering deposition is ≤3.0×10 -3 Pa.

[0034] In another aspect, the present application provides the use of any one of the multifunctional protective coatings described above in a coated product.

[0035] In some embodiments, the multifunctional protective coating serves as at least a portion of a protective coating on a coated article.

[0036] In another aspect, the present application provides a coated product, comprising a substrate and any one of the multifunctional protective coatings described above.

[0037] In some embodiments, the multifunctional protective coating is located on at least one side of the substrate.

[0038] In some embodiments, the surface material of the substrate is at least one of glass, plastic and silicon wafer.

[0039] In some embodiments, the coated product comprises a single or multiple multifunctional protective coatings. Optionally, the coated product further comprises a diamond-like carbon film coating and / or an anti-fingerprint coating.

[0040] Compared with the prior art, the present invention has the following advantages:

[0041] (1) The multifunctional protective coating of the present application has high refractive index, high nanohardness, high scratch resistance, low stress and high durability.

[0042] (2) The multifunctional protective coating of the present application can be used as a protective coating for coated products. It can be used alone as a protective coating for coated products, or it can be used together with other coatings to give the coated products high refractive index, high nanohardness, high scratch resistance, low stress and high durability.

[0043] (3) The preparation method of the multifunctional protective coating of the present application is simple to operate, has good repeatability, and is suitable for industrial application. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] In order to more clearly illustrate the specific implementation methods of the present application or the technical solutions in the prior art, the following is a brief introduction to the drawings required for use in the specific implementation methods or the description of the prior art. Obviously, the drawings described below are some implementation methods of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0045] FIG1 is a schematic diagram of an apparatus for preparing a multifunctional protective coating according to an embodiment of the present application;

[0046] Figure 2 shows the Si prepared in Example 1 of this application. 0.41 N 0.59 FTIR images of multifunctional protective coatings;

[0047] Figure 3 shows the Si prepared in Example 2 of this application. 0.39 N 0.61 FTIR images of multifunctional protective coatings;

[0048] Figure 4 shows the Si prepared in Example 5 of this application. 0.42 N 0.58 FTIR images of multifunctional protective coatings;

[0049] Figure 5 shows the Si prepared in Comparative Example 6 of this application. 0.36 N 0.64 FTIR spectrum of the multifunctional protective coating.

[0050] Reference numerals: 1 - vacuum chamber; 2 - sample stage; 3 - ion source; 4 - silicon target. DETAILED DESCRIPTION

[0051] The technical scheme of the present application will be clearly and completely described below in conjunction with the accompanying drawings and specific embodiments, but it will be understood by those skilled in the art that the following described embodiments are part of the present application's embodiments, rather than all of the embodiments, and are only used to illustrate the present application, and should not be considered as limiting the scope of the present application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of the present application. Those who do not specify specific conditions in the embodiments are carried out according to conventional conditions or the conditions recommended by the manufacturer. Those whose reagents or instruments are not specified as manufacturers are conventional products that can be purchased commercially.

[0052] In the description of this application, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., indicating orientations or positional relationships, are based on the orientations or positional relationships shown in the accompanying drawings and are intended solely to facilitate the description of this application and simplify the description. They do not indicate or imply that the devices or components referred to must have a specific orientation, be constructed, or operate in a specific orientation. Therefore, they should not be construed as limitations on this application. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0053] In the description of this application, it should be noted that, unless otherwise expressly specified or limited, the terms "mounted," "connected," and "connected" should be understood in a broad sense. For example, they can refer to fixed connections, detachable connections, or integral connections; mechanical connections or electrical connections; direct connections or indirect connections through an intermediate medium; and internal connections between two components. Those skilled in the art will understand the specific meanings of the above terms in this application based on the specific circumstances.

[0054] Through extensive research and data analysis, the inventors determined that the coating's refractive index falls within the realm of optical properties, hardness and scratch resistance fall within the realm of mechanical properties, and stress and durability fall within the realm of internal growth. These five parameters are distributed across three distinct research areas and are mutually constrained, with some exhibiting positive correlations and others negative. To achieve a coating with high refractive index, high nanohardness, high scratch resistance, low stress, and high durability simultaneously, it is necessary to combine these various coating parameters from multiple dimensions to find the optimal characteristic space.

[0055] First of all, from the perspective of the coating composition design, low coating absorption means less light loss. To achieve low absorption of the Si-N coating, it is necessary to ensure sufficient nitridation, that is, the N / Si atomic ratio in the Si-N coating is ≥1, forming a nitrogen-rich structural coating. From the perspective of the internal growth structure of the coating, the durability of the coating means the long-term use characteristic parameters of the coating. The Si-N coating can be divided into two types: hydrogen-containing components and hydrogen-free components. Since hydrogen has a single bond structure, its thermal stability is poor, resulting in the coating having a qualitative change problem during daily use. This indicates that the durability of the coating design is poor and it is not easy to be used as a surface coating for 3C products for a long time. Therefore, in order to improve the durability of the coating, the Si-N coating composition of this application is a hydrogen-free coating. Among them, the hydrogen-free coating does not mean that the coating is absolutely free of hydrogen atoms, but allows the coating to have a hydrogen content of ≤1% by atomic number.

[0056] For example, “Low hydrogen content stoichiometric silicon nitride films deposited by plasma-enhanced chemical vapor deposition, Parsons GN, et al., J. Appl. Phys., 70(3):1553-1560” describes a Si-N coating deposited by chemical vapor deposition. The peak position of the Fourier transform infrared spectrum of the Si-N coating is 820-870 cm -1 The corresponding half-wave peak width of the Fourier transform infrared spectrum is 190-210 cm -1 Through analysis, the Si-N coating contains hydrogen and is a Si-HN coating. Its Fourier transform infrared spectrum contains obvious hydrogen absorption peaks, such as 3330cm -1 NH absorption peak at 2140 cm -1 The Si-H absorption peak, the NH content is (1.6~15)×10 21 / cm 3 , the Si-H content is (0.8~16)×10 21 / cm 3 , it can be seen that the hydrogen content is greater than 1% in terms of atomic number. However, as mentioned above, since hydrogen has a single bond structure, its thermal stability is poor, resulting in the coating's quality change during daily use, which affects the coating's durability and is not suitable for use as a surface coating for 3C products.

[0057] Secondly, the refractive index of the coating is a characteristic parameter in the optical field of the coating. The refractive index of the coating directly reflects the densification characteristics of the coating. The density reflects the compactness of the atomic stacking, that is, the stacking structure between atoms or atomic groups; the tighter the atomic stacking, that is, the higher the density, the greater the refractive effect on light, that is, the higher the refractive index, so the refractive index can reflect the density of the coating. That is, the degree of densification of the coating is positively correlated with the density of the coating material. The higher the refractive index, the higher the degree of densification; the degree of densification of the coating is positively correlated with the nanohardness and scratch resistance of the coating, that is, the higher the degree of densification, the higher the nanohardness of the coating and the stronger the scratch resistance. In addition, the refractive index of the coating is also related to the composition of the coating. Under normal circumstances, Si that meets the ideal stoichiometric ratio x N y Coating and nitrogen-rich Si x N y The coating has a refractive index of less than 2.2 at a wavelength of 550 nm.

[0058] The coating's Fourier Transform Infrared spectroscopy (FTIR) half-wave peak width (Full Width at Half Maximum, FWHM) is a parameter of the coating's internal growth domain. Stress reflects the coating's brittleness, while durability reflects its ability to withstand long-term use. From the perspective of the coating's atomic growth structure, stress and durability can be characterized by the degree of distortion in the atomic bond angles, which can be quantified using FTIR-FWHM. This is positively correlated with stress and negatively correlated with durability. That is, the greater the degree of distortion in the atomic bond angles (the larger the FTIR-FWHM), the greater the stress and the worse the durability, and vice versa. Therefore, to achieve both low-stress and high-durability coatings, it is necessary to precisely control the degree of distortion in the atomic bond angles, that is, precisely control the FTIR-FWHM parameter.

[0059] At the same time, the degree of distortion of the atomic bonding angle is a microstructure, representing the degree to which the interatomic bonds are squeezed during the atomic nucleation process within the coating. The tighter the squeezing, the higher the macroscopic densification of the coating. This shows that the degree of distortion of the atomic bonding angle is related to the densification degree of the coating, and there is a positive correlation. The greater the degree of distortion of the atomic bonding angle, the higher the density, and vice versa. This further illustrates that within a certain Si-N coating composition range, it is necessary to simultaneously control the structural parameters of the degree of densification (i.e., refractive index) and the degree of distortion of the bonding angle (i.e., FTIR-FWHM).

[0060] For example, "Properties of Magnetron-Sputtered Silicon Nitride Films, T. Serikawa, et al, J. Electrochem. Soc., 131(12): 2928-2933" describes a Si-N coating that is mainly nitrogen-rich in composition. However, the refractive index of Si-N is low. As discussed above, the coating has poor density, and the FTIR peak is at 840 cm -1 , FTIR-FWHM is 370 cm -1 , FWHM is larger. As mentioned above, the atomic bonding energy of the coating is more distorted and the stress of the coating is larger.

[0061] Therefore, in order to realize the multifunctional protective coating of the present application with high refractive index, high nanohardness, high scratch resistance, low stress and high durability, it is necessary to accurately quantify and control the characteristic space of each parameter.

[0062] Based on this, the present application provides a multifunctional protective coating having a chemical formula of Si x N y The material meets the following characteristics:

[0063] (a) x and y are atomic ratios, and 0.39≤x≤0.43, 0.57≤y≤0.61;

[0064] (b) Fourier transform infrared spectrum with peak positions ranging from 838 to 875 cm -1 The half-wave peak width at the -1 ;

[0065] (c) The refractive index at 550 nm is 2.0 to 2.2;

[0066] (d) The hydrogen content, calculated by atomic number, is ≤ 1%.

[0067] The multifunctional protective coating of the present application has high refractive index, high nanohardness, high scratch resistance, low stress and high durability.

[0068] In the coating of the present application, the hydrogen content, calculated by atomic number, refers to the ratio of hydrogen atoms to the total number of silicon atoms, nitrogen atoms and hydrogen atoms.

[0069] Among them, the nanohardness of the multifunctional protective coating of the present application is 25~30GPa, and the scratch resistance meets the following requirements: a single layer can pass 200 steel wool tests, and a multi-layer can pass 3000 steel wool tests. The stress meets the following requirements: it can pass the 100-grid test, and the durability meets the following requirements: it can pass the 48h salt spray test and the 72h thermal shock test.

[0070] As in different embodiments of the present application, Si x N y In the formula (a), x may be selected from but not limited to 0.39, 0.40, 0.41, 0.42, 0.43 or a range consisting of any two thereof, and y may be selected from but not limited to 0.57, 0.58, 0.59, 0.60, 0.61 or a range consisting of any two thereof.

[0071] As in different embodiments of the present application, Si x N y The FTIR peak position range of the coating corresponding to the material can be selected from but not limited to 838 cm -1 、840cm -1 、845cm -1 , 850cm -1 , 855cm -1 、860cm -1 、865cm -1 、870cm -1 , 875cm -1 Or any two of them. Among them, the FTIR peak position refers to Si x N y The wave number corresponding to the maximum value of the main absorption peak in the FTIR of the coating corresponding to the material.

[0072] The peak position of FTIR is in the range of 838~875cm -1 The half-wave peak width corresponding to the absorption peak in the range is selected from but not limited to 247 cm -1 , 250cm -1 , 260cm -1 , 270cm -1 , 280cm -1 , 290cm -1 , 300cm -1 、310cm -1 、313cm -1 Or a range consisting of any two of them.

[0073] In the present application, conventional instruments and methods in the art can be used to obtain the infrared spectrum of the multifunctional protective coating, and the corresponding FTIR-FWHM can be obtained based on the infrared spectrum. For example, a Thermo Fisher IS50 Fourier transform infrared spectrometer can be used.

[0074] As in different embodiments of the present application, Si x N yThe refractive index of the coating corresponding to the material at 550 nm can be 2.0, 2.02, 2.04, 2.08, 2.1, 2.12, 2.14, 2.15, 2.18, 2.2, or a range consisting of any two thereof.

[0075] In some embodiments, the refractive index at 550 nm is between 2.04 and 2.13.

[0076] In some embodiments, the coating contains zero hydrogen.

[0077] In this application, whether the coating contains hydrogen can be determined by whether there is an absorption peak related to hydrogen in FTIR: if there is an absorption peak between 3230 and 3430 cm -1 2040~2240cm -1 1450~1650cm -1 1050~1250cm -1 If there is an absorption peak at any one or more positions of the coating, it means that the coating contains hydrogen. -1 2040~2240cm -1 1450~1650cm -1 1050~1250cm -1 If there is no absorption peak at all places, it means that the coating does not contain hydrogen or the hydrogen content is ≤1%.

[0078] In some embodiments, the thickness of the coating is 0.01 to 6.0 μm, optionally 0.27 to 1.3 μm, and further optionally 0.3 to 0.9 μm.

[0079] As in different embodiments of the present application, the thickness of the coating can be selected from but not limited to 0.01 μm, 0.02 μm, 0.05 μm, 0.08 μm, 0.1 μm, 0.2 μm, 0.5 μm, 0.8 μm, 1.0 μm, 1.5 μm, 2.0 μm, 2.5 μm, 3.0 μm, 3.5 μm, 4.0 μm, 4.5 μm, 5.0 μm, 5.5 μm, 6 μm or a range consisting of any two thereof.

[0080] By controlling the thickness of the coating within the above range, the multiple functions of the protective coating can be further exerted to ensure high refractive index, high nanohardness, high scratch resistance, low stress and high durability.

[0081] Another aspect of the present application provides a method for preparing a multifunctional protective coating, comprising the following steps:

[0082] The constituent elements of the multifunctional protective coating are deposited on at least a portion of the surface of the substrate in a preset proportion by physical vapor deposition to form the multifunctional protective coating.

[0083] Through physical vapor deposition, under vacuum conditions, Si is introduced into the sputtering area by vapor deposition and combined with N. The Si output power and nitrogen gas volume can be precisely controlled. x N y The x and y parameters in the , thereby obtaining a protective coating material that meets the component requirements of this application, and controlling the degree of distortion of the bond angle of atomic bonding and the degree of densification of the coating to control the various properties of the coating.

[0084] Furthermore, chemical vapor deposition (CVD) typically uses hydrogen-containing precursors to prepare SiN, which introduces hydrogen into the coating and is difficult to remove. In physical vapor deposition (PVD), in addition to the addition of hydrogen-containing reaction gases, the hydrogen in the coating mostly comes from residual gases in the background vacuum conditions, often appearing as impurities.

[0085] In some embodiments, the physical vapor deposition method is at least one of vacuum evaporation, sputtering, arc plasma plating, ion plating and molecular beam epitaxy.

[0086] In some embodiments, the sputtering coating is magnetron sputtering coating, and optionally, it is radio frequency magnetron sputtering coating, direct current magnetron sputtering coating, or radio frequency assisted direct current magnetron sputtering coating.

[0087] In some embodiments, a schematic diagram of an apparatus for preparing a multifunctional protective coating is shown in FIG1 . The apparatus shown in FIG1 includes a vacuum chamber 1, a sample stage 2, an ion source 3, and a silicon target 4. The silicon target 4 can be powered by a pulsed DC power supply, and the pulse duty cycle can be 20% to 90%.

[0088] As in different embodiments of the present application, the pulse duty cycle value can be selected from but not limited to 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or a range consisting of any two thereof.

[0089] In some embodiments, a multifunctional protective coating is formed by sputtering and depositing a silicon target on at least a portion of the surface of the substrate under the condition of introducing a mixed gas of argon and nitrogen-containing gas.

[0090] In some embodiments, the temperature of sputtering deposition is 30-330°C, such as but not limited to 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 150°C, 200°C, 250°C, 300°C, 330°C or any two thereof.

[0091] In some embodiments, the sputtering deposition time is 10 to 300 minutes, such as, but not limited to, 10 minutes, 20 minutes, 50 minutes, 80 minutes, 100 minutes, 150 minutes, 200 minutes, 250 minutes, 300 minutes, or any two thereof. The sputtering deposition time is adjusted based on the desired thickness of the multifunctional protective coating. The longer the sputtering deposition time, the thicker the resulting multifunctional protective coating. For example, when the deposition time is 110 minutes, the resulting multifunctional protective coating has a thickness of approximately 0.52 μm.

[0092] In some embodiments, the power density of the silicon target is 1.5 to 2.4 W / cm 2 , such as can be selected from but not limited to 1.5W / cm 2 , 1.6W / cm 2 , 1.7W / cm 2 , 1.8W / cm 2 , 1.9W / cm 2 , 2.0W / cm 2 , 2.1W / cm 2 , 2.2W / cm 2 , 2.3W / cm 2 , 2.4W / cm 2 Or a range consisting of any two of them.

[0093] In some embodiments, the bias voltage of the substrate is -180 to -20 V, such as but not limited to -180 V, -150 V, -120 V, -100 V, -80 V, -50 V, -20 V, or any two thereof.

[0094] In some embodiments, the background vacuum degree of the vacuum chamber used for sputtering deposition is ≤3.0×10 -3 The background vacuum degree of the vacuum chamber meets the above conditions, which can ensure the collision between sputtered particles and gas molecules, and also reduce the entry of impurities into gas molecules during the deposition process, so as to improve the purity and bonding strength of the multifunctional protective coating material of the present application.

[0095] In some embodiments, the total pressure of the mixed gas is 0.05-1.2 Pa, such as but not limited to 0.05 Pa, 0.1 Pa, 0.2 Pa, 0.5 Pa, 0.8 Pa, 1.0 Pa, 1.2 Pa or a range consisting of any two thereof.

[0096] It can be understood that argon and nitrogen-containing gas can be introduced into the vacuum chamber through a single path or mixed through a mixing cylinder and then enter the chamber. The purpose is to reduce the impurity content of the multifunctional protective coating material of the present application and improve its performance.

[0097] In some embodiments, the nitrogen-containing gas is nitrogen, and the gas ratio of argon to nitrogen is (0.61-0.71): 1. By adjusting the gas ratio of argon to nitrogen in the mixed gas, the performance of the multifunctional protective coating can be further adjusted.

[0098] As in different embodiments of the present application, the gas volume ratio of argon and nitrogen can be selected from but not limited to 0.61:1, 0.62:1, 0.63:1, 0.64:1, 0.65:1, 0.66:1, 0.67:1, 0.68:1, 0.69:1, 0.70:1, 0.71:1 or a range consisting of any two of them.

[0099] In some embodiments, the nitrogen gas flow rate is 56 to 300 sccm, such as but not limited to 56 sccm, 60 sccm, 80 sccm, 100 sccm, 150 sccm, 200 sccm, 250 sccm, 300 sccm or any two thereof.

[0100] In actual operation, “depositing the constituent elements of the multifunctional protective coating on at least a portion of the surface of the substrate in a preset proportion by physical vapor deposition to form the multifunctional protective coating” may specifically include the following steps: -3 A mixed gas containing argon and nitrogen is introduced into the vacuum chamber 1 of Pa, and the pressure in the vacuum chamber 1 is maintained at 0.05-1.2 Pa. The bias voltage is turned on and set to -180--20 V. The power density of the silicon target 4 is set to 1.5-2.4 W / cm 2 , depositing Si on at least a portion of the surface of the substrate x N y Coating; multifunctional protective coatings of different thicknesses can be obtained by regulating the sputtering deposition time.

[0101] In some embodiments, before sputtering and depositing the multifunctional protective coating on the substrate, a step of cleaning the substrate is also included. The cleaning step can be performed using conventional cleaning methods in the art.

[0102] In some embodiments, the cleaning process may include placing the substrate in deionized water for ultrasonic cleaning for 3 to 15 minutes, then drying the substrate with nitrogen gas before placing it on a sample stage in the vacuum chamber. The sample stage may be a rotatable sample stage.

[0103] In some embodiments, after the cleaning process, a single layer or multilayer film may be pre-deposited on the substrate surface before the multifunctional protective coating is deposited. Whether or not to pre-deposit the film and the specific type of the pre-deposited single layer or multilayer film can be adjusted and selected based on actual needs.

[0104] In another aspect, the present application provides the use of any one of the multifunctional protective coatings described above in a coated product.

[0105] In some embodiments, the multifunctional protective coating serves as at least a portion of a protective coating on a coated article.

[0106] In some embodiments, the coated products include but are not limited to 3C products.

[0107] In another aspect, the present application provides a coated product, comprising a substrate and any one of the above-mentioned multifunctional protective coatings.

[0108] In some embodiments, the multifunctional protective coating is disposed on at least one side of the substrate.

[0109] In some embodiments, the surface material of the substrate is at least one of glass, plastic, and silicon wafer.

[0110] In some embodiments, the coated article includes a single or multiple multifunctional protective coatings. Optionally, the coated article further includes a diamond-like carbon film coating (DLC coating) and / or an anti-fingerprint coating (AF coating).

[0111] The coated product may include only the multifunctional protective coating of the present application, or may additionally include other film layers. The multifunctional protective coating of the present application may be used in conjunction with the other film layers.

[0112] The test methods involved in this application are as follows:

[0113] 1. Fourier transform infrared spectroscopy (FTIR)

[0114] A Thermo Fisher IS50 Fourier transform infrared spectrometer was used, and a double-sided polished silicon wafer was used as the background subtraction substrate. -1 Wave number interval, test 4000~400cm -1 The absorption spectrum within the band is divided by the film thickness for thickness normalization. The peak position is the wave number corresponding to the maximum value of the main absorption peak in the absorption spectrum, and the half-wave width (FWHM) is the width of the wave number range corresponding to half of the maximum value of the main absorption peak.

[0115] 2. Scratch resistance test method

[0116] Use a Taber 5750 Linear Tribometer to rub the product surface with 10mm x 55mm steel wool. Set the load to 250g, the frequency to 60 cycles / min, the number of cycles to 10, and the stroke to 15mm. After the test, observe the product surface for any obvious scratches or wear.

[0117] Rating: Level 1 - No damage; Level 2 - No scratches visible to the naked eye; Level 3 - Minor scratches visible to the naked eye; Level 4 - Numerous scratches visible to the naked eye. Criteria: Level 1 is OK, acceptable; Levels 2-4 are NG, unacceptable.

[0118] Among them, for single layer (Si x N y ) The test times are 200 times, for the stack (Si x N y / DLC / AF) test times is 3000 times.

[0119] 3. Durability test method

[0120] A high temperature and high humidity test machine was used to conduct a 72-hour storage durability test in a high temperature and high humidity environment with a temperature of 65℃±1℃ and a humidity of 91% to 95% RH. A hot and cold shock test machine was used to conduct a 72-hour storage durability test in a temperature cycle environment of -40℃±1℃ / 1h to 75±2℃ / 1h. A salt spray test machine was used to conduct a 48-hour storage durability test in a salt spray environment with a temperature of 35℃ and a sodium chloride concentration of 5%. After the test, it was observed that the product coating had no peeling, the appearance was normal, and the optical properties were normal.

[0121] 4. Stress testing method

[0122] The stress is characterized by a 100-grid test. The 100-grid test in this application is based on the provisions of the GB / T 9286-2021 standard. The specific method is as follows: use a manual single-edged cutting knife to cut 10×10 1mm×1mm small grids on the coated area of ​​the sample surface, and use 3M610 adhesive tape to stick on the grid area. Within 5 minutes after sticking the tape, hold the suspended end of the tape and tear off the tape smoothly at an angle of nearly 60° within 0.5s to 1.0s. Determine the level according to the provisions of the GB / T9286-2021 standard, where level 0 is passed and levels 1 to 5 are failures.

[0123] 5. Hardness test method

[0124] The hardness of each film was tested using an NHT3 nanoindenter produced by Anton-Paar, Austria. It was equipped with a tetrahedral Berkvich indenter and the indentation depth was set to 100 nm. The load varied with the indentation depth. Five matrix points were tested for each sample and the average value was taken.

[0125] 6. EDX test method for coating composition

[0126] An energy dispersive X-ray (EDX) spectrometer (EDS) was used with a Hitachi Regulus 8230 scanning electron microscope. The relative intensities of all elements were corrected using the ZAF method. The electron acceleration voltage was 15 kilovolts, the beam current was 10 microamperes, and the sample magnification was 200x. Ten points were measured for each sample, and the average was calculated.

[0127] In the embodiments, “hydrogen-free” means that the coating absolutely does not contain hydrogen atoms, or the hydrogen content is ≤1% by atomic number.

[0128] Example 1

[0129] This embodiment provides a multifunctional protective coating and a preparation method thereof. The chemical composition of the multifunctional protective coating is Si 0.41 N 0.59 , and its preparation method comprises the following steps:

[0130] (1) Pre-treatment: 71mm × 155mm in length and width, with a transmittance of T 400～700 =92%, Corning GG3 high aluminosilicate glass with a pencil hardness of 9H, Mitsubishi MB6001UR PMMA / PC composite plastic with a pencil hardness of 3H, and 20mm×20mm silicon wafer samples were ultrasonically cleaned in deionized water for 15 minutes, dried with N2, and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 3×10 -3 Pa.

[0131] (2) Deposition of protective coating: Turn on the sample stage turret, set the rotation speed to 4 revolutions per minute, adjust the distance from the sample stage to the target surface to 10 cm, use a pulsed DC power supply to energize the Si target, introduce Ar and N2 gas, set the N2 gas flow rate to 60 sccm, set the gas volume to maintain the Ar to N2 gas ratio of 0.71:1, maintain the pressure in the furnace at 0.09 Pa, and set the power density of the Si target to 2.4 W / cm 2 , the pulse duty cycle is set to 20%, and the Si-N protective coating is deposited. By controlling the film formation time, the obtained film thickness is 291nm.

[0132] The multifunctional protective coating Si prepared by the above method 0.41 N 0.59 FTIR test was performed on the silicon wafer, as shown in Figure 2, showing that its FTIR peak position is 838cm -1 , the corresponding half-wave peak width is 297cm -1 , at 3230~3430cm -1 2040~2240cm -1 1450~1650cm -1 1050~1250cm-1 There is no absorption peak related to hydrogen, indicating that the coating does not contain hydrogen.

[0133] The multifunctional protective coating prepared in this embodiment has a refractive index of 2.13 at 550 nm, a nanohardness value of 30 GPa for the film layer on the GG3 high alumina silicate glass substrate, and a Mohs hardness grade of 6 for the film layer on the GG3 high alumina silicate glass substrate.

[0134] The film layer on the GG3 high alumina silicate glass substrate can pass the steel wool test 200 times.

[0135] A 100-grid test was conducted on the film layer on the GG3 high-alumina-silica glass substrate. The surface appearance was normal, the cutting edges were smooth and complete, and there was no coating layer falling off, which can meet the Level 0 judgment level in GB / T 9286-2021.

[0136] The durability tests of the film layer on the GG3 high-alumina-silica glass substrate and the film layer on the PMMA / PC composite board plastic were carried out, and the films were able to pass the 72h high-temperature and high-humidity storage test, the 72h temperature shock test, and the 48h salt spray test.

[0137] The above test results show that the protective coating of this embodiment has the multifunctional characteristics of high refractive index, high hardness, scratch resistance, low stress, and high durability.

[0138] Example 2

[0139] This embodiment provides a multifunctional protective coating and a preparation method thereof. The chemical composition of the multifunctional protective coating is Si 0.39 N 0.61 , and its preparation method comprises the following steps:

[0140] (1) Pre-treatment: 71mm × 155mm in length and width, with a transmittance of T 400～700 = 92%, GG3 high aluminosilicate glass with a pencil hardness of 9H, PMMA / PC composite plastic MB6001UR with a pencil hardness of 3H, and 20mm×20mm silicon wafer samples were ultrasonically cleaned in deionized water for 15min, dried with N2, and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 3×10 -3 Pa.

[0141] (2) Deposition of protective coating: Turn on the sample stage turret, set the rotation speed to 4 revolutions per minute, adjust the distance from the sample stage to the target surface to 10 cm, use a pulsed DC power supply to energize the Si target, introduce Ar and N2 gas, set the N2 gas flow rate to 66 sccm, set the gas volume to maintain the Ar to N2 gas ratio of 0.61:1, maintain the furnace pressure at 0.09 Pa, and set the power density of the Si target to 2.4 W / cm 2, the pulse duty cycle is set to 60%, and the Si-N protective coating is deposited. By controlling the film formation time, the obtained film thickness is 273nm.

[0142] The multifunctional protective coating Si prepared by the above method 0.39 N 0.61 FTIR test was performed on the silicon wafer, as shown in Figure 3, showing that its FTIR peak position is 838cm -1 , the corresponding half-wave peak width is 313cm -1 , at 3230~3430cm -1 2040~2240cm -1 1450~1650cm -1 1050~1250cm -1 There is no absorption peak related to hydrogen, indicating that the coating does not contain hydrogen.

[0143] The multifunctional protective coating prepared in this embodiment has a refractive index of 2.04 at 550 nm, a nanohardness value of 27 GPa for the film layer on the GG3 high alumina silicate glass substrate, and a Mohs hardness grade of 7 for the film layer on the GG3 high alumina silicate glass substrate.

[0144] The film layer on the GG3 high alumina silicate glass substrate can pass the steel wool test 200 times.

[0145] A 100-grid test was performed on the film layer on the GG3 high-alumina-silica glass substrate. The surface appearance was normal, the cut edges were smooth and complete, and there was no coating layer falling off. It can reach the Level 0 judgment level in GB / T 9286-2021 and can pass the 100-grid test.

[0146] The durability tests of the film layer on the GG3 high-alumina-silica glass substrate and the film layer on the PMMA / PC composite board plastic were carried out, and the films were able to pass the 72h high-temperature and high-humidity storage test, the 72h temperature shock test, and the 48h salt spray test.

[0147] The above test results show that the protective coating of this embodiment has the multifunctional characteristics of high refractive index, high hardness, scratch resistance, low stress, and high durability.

[0148] Example 3

[0149] This embodiment provides a multifunctional protective coating and a preparation method thereof. The chemical composition of the multifunctional protective coating is Si 0.43 N 0.57 , and its preparation method comprises the following steps:

[0150] (1) Pre-treatment: 71mm × 155mm in length and width, with a transmittance of T 400～700= 92%, GG3 high aluminosilicate glass with a pencil hardness of 9H, PMMA / PC composite plastic MB6001UR with a pencil hardness of 3H, and 20mm×20mm silicon wafer samples were ultrasonically cleaned in deionized water for 15min, dried with N2, and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 3×10 -3 Pa.

[0151] (2) Deposition of protective coating: Turn on the sample stage turret, set the rotation speed to 4 revolutions per minute, adjust the distance from the sample stage to the target surface to 10 cm, use a pulsed DC power supply to energize the Si target, introduce Ar and N2 gas, set the N2 gas flow rate to 56 sccm, set the gas volume to maintain the Ar to N2 gas ratio of 0.67:1, maintain the furnace pressure at 0.09 Pa, and set the power density of the Si target to 2.4 W / cm 2 , the pulse duty cycle is set to 60%, and the Si-N protective coating is deposited. By controlling the film formation time, the obtained film thickness is 914nm.

[0152] The multifunctional protective coating Si prepared by the above method 0.43 N 0.57 FTIR test of silicon wafer shows that its FTIR peak is 867cm -1 , the corresponding half-wave peak width is 288cm -1 , at 3230~3430cm -1 2040~2240cm -1 1450~1650cm -1 1050~1250cm -1 There is no absorption peak related to hydrogen, indicating that the coating does not contain hydrogen.

[0153] The multifunctional protective coating prepared in this embodiment has a refractive index of 2.08 at 550 nm, a nanohardness value of 29 GPa for the film layer on the GG3 high-alumina-silica glass substrate, and a Mohs hardness grade of 6 for the film layer on the GG3 high-alumina-silica glass substrate.

[0154] The film layer on the GG3 high alumina silicate glass substrate can pass the steel wool test 200 times.

[0155] A 100-grid test was conducted on the film layer on the GG3 high-alumina-silica glass substrate. The surface appearance was normal, the cutting edges were smooth and complete, and there was no coating layer falling off, which can meet the Level 0 judgment level in GB / T 9286-2021.

[0156] The durability tests of the film layer on the GG3 high-alumina-silica glass substrate and the film layer on the PMMA / PC composite board plastic were carried out, and the films were able to pass the 72h high-temperature and high-humidity storage test, the 72h temperature shock test, and the 48h salt spray test.

[0157] The above test results show that the protective coating of this embodiment has the multifunctional characteristics of high refractive index, high hardness, scratch resistance, low stress, and high durability.

[0158] Example 4

[0159] This embodiment provides a multifunctional protective coating and a preparation method thereof. The chemical composition of the multifunctional protective coating is Si 0.40 N 0.60 , and its preparation method comprises the following steps:

[0160] (1) Pre-treatment: 71mm × 155mm in length and width, with a transmittance of T 400～700 = 92%, GG3 high aluminosilicate glass with a pencil hardness of 9H, PMMA / PC composite plastic MB6001UR with a pencil hardness of 3H, and 20mm×20mm silicon wafer samples were ultrasonically cleaned in deionized water for 15min, dried with N2, and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 3×10 -3 Pa.

[0161] (2) Deposition of protective coating: Turn on the sample stage turret, set the rotation speed to 4 revolutions per minute, adjust the distance from the sample stage to the target surface to 10 cm, use a pulsed DC power supply to energize the Si target, introduce Ar and N2 gas, set the N2 gas flow rate to 63 sccm, set the gas volume to maintain the Ar to N2 gas ratio of 0.61:1, maintain the furnace pressure at 0.09 Pa, and set the power density of the Si target to 2.4 W / cm 2 , the pulse duty cycle is set to 60%, and the Si-N protective coating is deposited. By controlling the film formation time, the obtained film thickness is 284nm.

[0162] The multifunctional protective coating Si prepared by the above method 0.40 N 0.60 FTIR test of silicon wafer shows that its FTIR peak is 839cm -1 , the corresponding half-wave peak width is 248cm -1 , at 3230~3430cm -1 2040~2240cm -1 1450~1650cm -1 1050~1250cm -1 There is no absorption peak related to hydrogen, indicating that the coating does not contain hydrogen.

[0163] The multifunctional protective coating prepared in this embodiment has a refractive index of 2.04 at 550 nm, a nanohardness value of 25 GPa for the film layer on the GG3 high alumina silicate glass substrate, and a Mohs hardness grade of 7 for the film layer on the GG3 high alumina silicate glass substrate.

[0164] The film layer on the GG3 high alumina silicate glass substrate can pass the steel wool test 200 times.

[0165] A 100-grid test was conducted on the film layer on the GG3 high-alumina-silica glass substrate. The surface appearance was normal, the cutting edges were smooth and complete, and there was no coating layer falling off, which can meet the Level 0 judgment level in GB / T 9286-2021.

[0166] The durability tests of the film layer on the GG3 high-alumina-silica glass substrate and the film layer on the PMMA / PC composite board plastic were carried out, and the films were able to pass the 72h high-temperature and high-humidity storage test, the 72h temperature shock test, and the 48h salt spray test.

[0167] The above test results show that the protective coating of this embodiment has the multifunctional characteristics of high refractive index, high hardness, scratch resistance, low stress, and high durability.

[0168] Example 5

[0169] This embodiment provides a multifunctional protective coating and a preparation method thereof. The chemical composition of the multifunctional protective coating is Si 0.42 N 0.58 , and its preparation method comprises the following steps:

[0170] (1) Pre-treatment: 71mm × 155mm in length and width, with a transmittance of T 400～700 = 92%, GG3 high aluminosilicate glass with a pencil hardness of 9H, PMMA / PC composite plastic MB6001UR with a pencil hardness of 3H, and 20mm×20mm silicon wafer samples were ultrasonically cleaned in deionized water for 15min, dried with N2, and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 3×10 -3 Pa.

[0171] (2) Deposition of protective coating: Turn on the sample stage turret, set the rotation speed to 4 revolutions per minute, adjust the distance from the sample stage to the target surface to 10 cm, use a pulsed DC power supply to energize the Si target, introduce Ar and N2 gas, set the N2 gas flow rate to 58 sccm, set the gas volume to maintain the Ar to N2 gas ratio of 0.67:1, maintain the pressure in the furnace at 0.09 Pa, and set the power density of the Si target to 2.4 W / cm 2 , the pulse duty cycle is set to 60%, and the Si-N protective coating is deposited. By controlling the film formation time, the obtained film thickness is 311 nm.

[0172] The multifunctional protective coating Si prepared by the above method 0.42 N 0.58 FTIR test was performed on the silicon wafer, as shown in Figure 4, showing that its FTIR peak position is 838cm -1, the corresponding half-wave peak width is 247cm -1 , at 3230~3430cm -1 2040~2240cm -1 1450~1650cm -1 1050~1250cm -1 There is no absorption peak related to hydrogen, indicating that the coating does not contain hydrogen.

[0173] The multifunctional protective coating prepared in this embodiment has a refractive index of 2.06 nm at 550 nm, a nanohardness value of 26 GPa for the film layer on the GG3 high-alumina-silica glass substrate, and a Mohs hardness grade of 7 for the film layer on the GG3 high-alumina-silica glass substrate.

[0174] The film layer on the GG3 high alumina silicate glass substrate can pass the steel wool test 200 times.

[0175] A 100-grid test was conducted on the film layer on the GG3 high-alumina-silica glass substrate. The surface appearance was normal, the cutting edges were smooth and complete, and there was no coating layer falling off, which can meet the Level 0 judgment level in GB / T 9286-2021.

[0176] The durability tests of the film layer on the GG3 high-alumina-silica glass substrate and the film layer on the PMMA / PC composite board plastic were carried out, and the films were able to pass the 72h high-temperature and high-humidity storage test, the 72h temperature shock test, and the 48h salt spray test.

[0177] The above test results show that the protective coating of this embodiment has the multifunctional characteristics of high refractive index, high hardness, scratch resistance, low stress, and high durability.

[0178] Example 6

[0179] This embodiment provides a multifunctional protective coating and a preparation method thereof. The chemical composition of the multifunctional protective coating is Si 0.41 N 0.59 , and its preparation method comprises the following steps:

[0180] (1) Pre-treatment: 71mm × 155mm in length and width, with a transmittance of T 400～700 = 92%, GG3 high aluminosilicate glass with a pencil hardness of 9H, PMMA / PC composite plastic MB6001UR with a pencil hardness of 3H, and 20mm×20mm silicon wafer samples were ultrasonically cleaned in deionized water for 15min, dried with N2, and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 3×10 -3 Pa.

[0181] (2) Deposition of protective coating: Turn on the sample stage turret, set the rotation speed to 4 revolutions per minute, adjust the distance from the sample stage to the target surface to 10 cm, use a pulsed DC power supply to energize the Si target, introduce Ar and N2 gas, set the N2 gas flow rate to 60 sccm, set the gas volume to maintain the Ar to N2 gas ratio of 0.71:1, maintain the pressure in the furnace at 0.09 Pa, and set the power density of the Si target to 2.4 W / cm 2 , the pulse duty cycle is set to 90%, and the Si-N protective coating is deposited. By controlling the film formation time, the obtained film thickness is 1348nm.

[0182] The multifunctional protective coating Si prepared by the above method 0.41 N 0.59 FTIR test of silicon wafer shows that its FTIR peak is 875cm -1 , the corresponding half-wave peak width is 301cm -1 , at 3230~3430cm -1 2040~2240cm -1 1450~1650cm -1 1050~1250cm -1 There is no absorption peak related to hydrogen, indicating that the coating does not contain hydrogen.

[0183] The multifunctional protective coating prepared in this embodiment has a refractive index of 2.08 nm at 550 nm, a nanohardness value of 28 GPa for the film layer on the GG3 high-alumina-silica glass substrate, and a Mohs hardness grade of 5 for the film layer on the GG3 high-alumina-silica glass substrate.

[0184] The film layer on the GG3 high alumina silicate glass substrate can pass the steel wool test 200 times.

[0185] A 100-grid test was conducted on the film layer on the GG3 high-alumina-silica glass substrate. The surface appearance was normal, the cutting edges were smooth and complete, and there was no coating layer falling off, which can meet the Level 0 judgment level in GB / T 9286-2021.

[0186] The durability tests of the film layer on the GG3 high-alumina-silica glass substrate and the film layer on the PMMA / PC composite board plastic were carried out, and the films were able to pass the 72h high-temperature and high-humidity storage test, the 72h temperature shock test, and the 48h salt spray test.

[0187] The above test results show that the protective coating of this embodiment has the multifunctional characteristics of high refractive index, high hardness, scratch resistance, low stress, and high durability.

[0188] Example 7

[0189] This embodiment provides a composite protective coating and a preparation method thereof, comprising a multifunctional protective coating, a DLC coating and an AF coating arranged in a stacked manner, wherein the chemical composition of the multifunctional protective coating is Si 0.41 N 0.59 , the preparation method comprises the following steps:

[0190] (1) Pre-treatment: 71mm × 155mm in length and width, with a transmittance of T 400～700 = 92%, GG3 high aluminosilicate glass with a pencil hardness of 9H, PMMA / PC composite plastic MB6001UR with a pencil hardness of 3H, and 20mm×20mm silicon wafer samples were ultrasonically cleaned in deionized water for 15min, dried with N2, and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 3×10 -3 Pa.

[0191] (2) Deposition of protective coating: First, turn on the sample stage turret and set the rotation speed to 4 revolutions per minute. Adjust the distance from the sample stage to the target surface to 10 cm. Use a pulsed DC power supply to energize the Si target. Introduce Ar and N2 gas. Set the N2 gas flow rate to 60 sccm. Set the gas volume to maintain the Ar to N2 gas ratio at 0.71:1. Maintain the pressure in the furnace at 0.09 Pa. Set the power density of the Si target to 2.4 W / cm 2 The pulse duty cycle was set to 20% to deposit a Si-N protective coating. By controlling the film formation time, the resulting film thickness was 291nm. Ar and C2H2 gases were then introduced, with the C2H2 flow rate set to 400sccm. The gas volume was set to maintain a 1:1 Ar to C2H2 ratio, the furnace pressure was maintained at 0.8Pa, and the bias duty cycle was set to 75%. A DLC coating was deposited, and by controlling the film formation time, the resulting film thickness was 20nm. Finally, a 20nm anti-fingerprint hydrophobic AF coating was deposited using a resistive evaporation source by controlling the film formation time.

[0192] In the composite protective coating prepared by the above method, the multifunctional protective coating Si 0.41 N 0.59 The water contact angle of the composite film layer on the GG3 high alumina silica glass substrate was tested to be 115°, the nano hardness value of the composite film layer on the GG3 high alumina silica glass substrate was tested to be 25 GPa, the friction coefficient was 0.16, and the Mohs hardness grade of the composite film layer on the GG3 high alumina silica glass substrate was tested to be 8.

[0193] The composite film layer on the GG3 high alumina silicate glass substrate can pass the steel wool test 3000 times.

[0194] A 100-grid test was conducted on the composite film layer on the GG3 high-alumina-silica glass substrate. The surface appearance was normal, the cutting edges were smooth and complete, and there was no coating layer falling off, which can meet the Level 0 judgment level in GB / T 9286-2021.

[0195] Durability tests are conducted on the composite film layer on the GG3 high-alumina-silica glass substrate and the composite film layer on the PMMA / PC composite board plastic, and the films can pass the 72h high-temperature and high-humidity storage test, the 72h temperature shock test, and the 48h salt spray test.

[0196] The above test results show that the protective coating of this embodiment has the multifunctional characteristics of high refractive index, high hardness, scratch resistance, low stress, and high durability.

[0197] Example 8

[0198] This embodiment provides a composite protective coating and a preparation method thereof, comprising a multifunctional protective coating, a DLC coating and an AF coating arranged in a stacked manner, wherein the chemical composition of the multifunctional protective coating is Si 0.43 N 0.57 , the preparation method comprises the following steps:

[0199] (1) Pre-treatment: 71mm × 155mm in length and width, with a transmittance of T 400～700 = 92%, GG3 high aluminosilicate glass with a pencil hardness of 9H, PMMA / PC composite plastic MB6001UR with a pencil hardness of 3H, and 20mm×20mm silicon wafer samples were ultrasonically cleaned in deionized water for 15min, dried with N2, and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 3×10 -3 Pa.

[0200] (2) Deposition of protective coating: First, turn on the sample stage turret and set the rotation speed to 4 revolutions per minute. Adjust the distance from the sample stage to the target surface to 10 cm. Use a pulsed DC power supply to energize the Si target. Introduce Ar and N2 gas. Set the N2 gas flow rate to 56 sccm. Set the gas volume to maintain the Ar to N2 gas ratio at 0.67:1. Maintain the pressure in the furnace at 0.09 Pa. Set the power density of the Si target to 2.4 W / cm 2 The pulse duty cycle was set to 60% to deposit a Si-N protective coating. By controlling the film formation time, the resulting film thickness was 517nm. Ar and C2H2 gases were then introduced, with the C2H2 flow rate set to 400sccm. The gas volume was set to maintain a 1:1 Ar to C2H2 ratio, the furnace pressure was maintained at 0.8Pa, and the bias duty cycle was set to 75%. A DLC coating was deposited. By controlling the film formation time, the resulting film thickness was 20nm. Finally, a 20nm anti-fingerprint hydrophobic AF coating was deposited using a resistive evaporation source by controlling the film formation time.

[0201] In the composite protective coating prepared by the above method, the multifunctional protective coating Si 0.43 N 0.57 FTIR test of silicon wafer shows that its FTIR peak is 848cm -1 , the corresponding half-wave peak width is 273cm -1 , at 3230~3430cm -1 2040~2240cm -1 1450~ 1650cm -1 1050~1250cm -1 There is no absorption peak related to hydrogen, indicating that the coating does not contain hydrogen.

[0202] The water contact angle of the composite film layer on the GG3 high alumina silica glass substrate was tested to be 114°, the nanohardness value of the composite film layer on the GG3 high alumina silica glass substrate was tested to be 23 GPa, the friction coefficient was 0.17, and the Mohs hardness grade of the composite film layer on the GG3 high alumina silica glass substrate was tested to be 9.

[0203] The composite film layer on the GG3 high alumina silicate glass substrate can pass the steel wool test 3000 times.

[0204] A 100-grid test was conducted on the composite film layer on the GG3 high-alumina-silica glass substrate. The surface appearance was normal, the cutting edges were smooth and complete, and there was no coating layer falling off, which can meet the Level 0 judgment level in GB / T 9286-2021.

[0205] Durability tests are conducted on the composite film layer on the GG3 high-alumina-silica glass substrate and the composite film layer on the PMMA / PC composite board plastic, and the films can pass the 72h high-temperature and high-humidity storage test, the 72h temperature shock test, and the 48h salt spray test.

[0206] The above test results show that the protective coating of this embodiment has the multifunctional characteristics of high refractive index, high hardness, scratch resistance, low stress, and high durability.

[0207] Example 9

[0208] This embodiment provides a composite protective coating and a preparation method thereof, comprising a multifunctional protective coating, a DLC coating and an AF coating arranged in a stacked manner, wherein the chemical composition of the multifunctional protective coating is Si 0.41 N 0.59 , the preparation method comprises the following steps:

[0209] (1) Pre-treatment: 71mm × 155mm in length and width, with a transmittance of T 400～700= 92%, GG3 high aluminosilicate glass with a pencil hardness of 9H, PMMA / PC composite plastic MB6001UR with a pencil hardness of 3H, and 20mm×20mm silicon wafer samples were ultrasonically cleaned in deionized water for 15min, dried with N2, and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 3×10 -3 Pa.

[0210] (2) Deposition of protective coating: First, turn on the sample stage turret and set the rotation speed to 4 revolutions per minute. Adjust the distance from the sample stage to the target surface to 10 cm. Use a pulsed DC power supply to energize the Si target. Introduce Ar and N2 gas. Set the N2 gas flow rate to 60 sccm. Set the gas volume to maintain the Ar to N2 gas ratio at 0.71:1. Maintain the pressure in the furnace at 0.09 Pa. Set the power density of the Si target to 2.4 W / cm 2 The pulse duty cycle was set to 90% to deposit a Si-N protective coating. By controlling the film formation time, the resulting film thickness was 1348nm. Ar and C2H2 gases were then introduced, with the C2H2 flow rate set to 400sccm. The gas volume was set to maintain a 1:1 Ar to C2H2 ratio, the furnace pressure was maintained at 0.8Pa, and the bias duty cycle was set to 75%. A DLC coating was deposited, and by controlling the film formation time, the resulting film thickness was 20nm. Finally, a 20nm anti-fingerprint hydrophobic AF coating was deposited using a resistive evaporation source by controlling the film formation time.

[0211] In the composite protective coating prepared by the above method, the multifunctional protective coating Si 0.41 N 0.59 The water contact angle of the composite film layer on the GG3 high alumina silica glass substrate was tested to be 115°, the nano hardness value of the composite film layer on the GG3 high alumina silica glass substrate was tested to be 26 GPa, the friction coefficient was 0.17, and the Mohs hardness grade of the composite film layer on the GG3 high alumina silica glass substrate was tested to be 8.

[0212] The composite film layer on the GG3 high alumina silicate glass substrate can pass the steel wool test 3000 times.

[0213] A 100-grid test was conducted on the composite film layer on the GG3 high-alumina-silica glass substrate. The surface appearance was normal, the cutting edges were smooth and complete, and there was no coating layer falling off, which can meet the Level 0 judgment level in GB / T 9286-2021.

[0214] Durability tests are conducted on the composite film layer on the GG3 high-alumina-silica glass substrate and the composite film layer on the PMMA / PC composite board plastic, and the films can pass the 72h high-temperature and high-humidity storage test, the 72h temperature shock test, and the 48h salt spray test.

[0215] The above test results show that the protective coating of this embodiment has the multifunctional characteristics of high refractive index, high hardness, scratch resistance, low stress, and high durability.

[0216] Comparative Example 1

[0217] Comparative Example 1 provides a coating and a preparation method thereof, wherein the chemical composition of the coating is Si 0.36 N 0.64 , and its preparation method comprises the following steps:

[0218] (1) Pre-treatment: 71mm × 155mm in length and width, with a transmittance of T 400～700 = 92%, GG3 high aluminosilicate glass with a pencil hardness of 9H, PMMA / PC composite plastic MB6001UR with a pencil hardness of 3H, and 20mm×20mm silicon wafer samples were ultrasonically cleaned in deionized water for 15min, dried with N2, and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 3×10 -3 Pa.

[0219] (2) Deposition of protective coating: Turn on the sample stage turret, set the rotation speed to 4 revolutions per minute, adjust the distance from the sample stage to the target surface to 10 cm, use a pulsed DC power supply to energize the Si target, introduce Ar and N2 gas, set the N2 gas flow rate to 280 sccm, set the gas volume to maintain the Ar to N2 gas ratio of 0.67:1, maintain the furnace pressure at 0.36 Pa, and set the power density of the Si target to 2.4 W / cm 2 , the pulse duty cycle is set to 60%, and the Si-N protective coating is deposited. By controlling the film formation time, the obtained film thickness is 240nm.

[0220] The coating prepared by the above method is Si 0.36 N 0.64 FTIR test of silicon wafer shows that its FTIR peak is 841cm -1 , the corresponding half-wave peak width is 351cm -1 , at 3230~3430cm -1 2040~2240cm -1 1450~1650cm -1 1050~1250cm -1 There is no absorption peak related to hydrogen, indicating that the coating does not contain hydrogen.

[0221] The refractive index of the protective coating layer prepared in Comparative Example 1 at 550 nm is 1.96 nm, the nanohardness value of the film layer on the GG3 high alumina silicate glass substrate is 21 GPa, and the Mohs hardness grade of the film layer on the GG3 high alumina silicate glass substrate is 4.

[0222] The film layer on the GG3 high alumina silicate glass substrate was subjected to a steel wool test and failed the test (200 test results NG).

[0223] A 100-grid test was performed on the film layer on the GG3 high-alumina-silica glass substrate. Small debris was found at the intersection of the cutting lines, and the peeling area was less than 5% of the total area, reaching the Level 1 judgment level in GB / T 9286-2021. The test failed.

[0224] Durability tests were conducted on the film layer on the GG3 high-alumina-silica glass substrate and the film layer on the PMMA / PC composite board plastic. After 72 hours of high-temperature and high-humidity storage test, 72 hours of temperature shock test, and 48 hours of salt spray test, the coating showed a certain degree of shedding and failed the test.

[0225] Comparative Example 2

[0226] Comparative Example 2 provides a coating and a preparation method thereof, wherein the chemical composition of the coating is Si 0.44 N 0.56 , and its preparation method comprises the following steps:

[0227] (1) Pre-treatment: 71mm × 155mm in length and width, with a transmittance of T 400～700 = 92%, GG3 high aluminosilicate glass with a pencil hardness of 9H, PMMA / PC composite plastic MB6001UR with a pencil hardness of 3H, and 20mm×20mm silicon wafer samples were ultrasonically cleaned in deionized water for 15min, dried with N2, and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 3×10 -3 Pa.

[0228] (2) Deposition of protective coating: Turn on the sample stage turret, set the rotation speed to 4 revolutions per minute, adjust the distance from the sample stage to the target surface to 10 cm, use a pulsed DC power supply to energize the Si target, introduce Ar and N2 gas, set the N2 gas flow rate to 240 sccm, set the gas volume to maintain the Ar to N2 gas ratio of 0.67:1, maintain the pressure in the furnace at 0.34 Pa, and set the power density of the Si target to 2.4 W / cm 2 , the pulse duty cycle is set to 60%, and the Si-N protective coating is deposited. By controlling the film formation time, the obtained film thickness is 731nm.

[0229] The coating prepared by the above method is Si 0.44 N 0.56 FTIR test of silicon wafer shows that its FTIR peak is 859cm -1 , the corresponding half-wave peak width is 285cm -1 , at 3230~3430cm -1 2040~2240cm -11450~1650cm -1 1050~1250cm -1 There is no absorption peak related to hydrogen, indicating that the coating does not contain hydrogen.

[0230] The protective coating prepared in Comparative Example 2 has a refractive index of 1.97 nm at 550 nm, a nanohardness value of 19 GPa for the film layer on the GG3 high alumina silicate glass substrate, and a Mohs hardness grade of 3 for the film layer on the GG3 high alumina silicate glass substrate.

[0231] The film layer on the GG3 high alumina silicate glass substrate was subjected to a steel wool test and failed the test (200 test results NG).

[0232] A 100-grid test was performed on the film layer on the GG3 high-alumina-silica glass substrate. Small debris was found at the intersection of the cutting lines, and the peeling area was less than 5% of the total area, reaching the Level 1 judgment level in GB / T 9286-2021. The test failed.

[0233] The durability tests of the film layer on the GG3 high-alumina-silica glass substrate and the film layer on the PMMA / PC composite board plastic were carried out, and the films were able to pass the 72h high-temperature and high-humidity storage test, the 72h temperature shock test, and the 48h salt spray test.

[0234] Comparative Example 3

[0235] Comparative Example 3 provides a coating and a preparation method thereof, wherein the chemical composition of the coating is Si 0.37 N 0.63 , and its preparation method comprises the following steps:

[0236] (1) Pre-treatment: 71mm × 155mm in length and width, with a transmittance of T 400～700 = 92%, GG3 high aluminosilicate glass with a pencil hardness of 9H, PMMA / PC composite plastic MB6001UR with a pencil hardness of 3H, and 20mm×20mm silicon wafer samples were ultrasonically cleaned in deionized water for 15min, dried with N2, and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 3×10 -3 Pa.

[0237] (2) Deposition of protective coating: Turn on the sample stage turret, set the rotation speed to 4 revolutions per minute, adjust the distance from the sample stage to the target surface to 10 cm, use a pulsed DC power supply to energize the Si target, introduce Ar and N2 gas, set the N2 gas flow rate to 260 sccm, set the gas volume to maintain the Ar to N2 gas ratio of 0.67:1, maintain the furnace pressure at 0.36 Pa, and set the power density of the Si target to 2.4 W / cm 2 , the pulse duty cycle is set to 60%, and the Si-N protective coating is deposited. By controlling the film formation time, the obtained film thickness is 313 nm.

[0238] The coating prepared by the above method is Si 0.37 N 0.63 FTIR test of silicon wafer shows that its FTIR peak is 843cm -1 , the corresponding half-wave peak width is 355cm -1 , at 3230~3430cm -1 2040~2240cm -1 1450~1650cm -1 1050~1250cm -1 There is no absorption peak related to hydrogen, indicating that the coating does not contain hydrogen.

[0239] The protective coating prepared in Comparative Example 3 has a refractive index of 1.96 at 550 nm, a nanohardness value of 20 GPa for the film layer on the GG3 high alumina silicate glass substrate, and a Mohs hardness grade of 4 for the film layer on the GG3 high alumina silicate glass substrate.

[0240] The film layer on the GG3 high alumina silicate glass substrate was subjected to a steel wool test and failed the test (200 test results NG).

[0241] A 100-grid test was performed on the film layer on the GG3 high-alumina-silica glass substrate. Small debris was found at the intersection of the cutting lines, and the peeling area was less than 5% of the total area, reaching the Level 1 judgment level in GB / T 9286-2021. The test failed.

[0242] Durability tests were conducted on the film layer on the GG3 high-alumina-silica glass substrate and the film layer on the PMMA / PC composite board plastic. After 72 hours of high-temperature and high-humidity storage test, 72 hours of temperature shock test, and 48 hours of salt spray test, the coating showed a certain degree of shedding and failed the test.

[0243] Comparative Example 4

[0244] Comparative Example 4 provides a coating and a preparation method thereof, wherein the chemical composition of the coating is Si 0.35 N 0.65 , and its preparation method comprises the following steps:

[0245] (1) Pre-treatment: 71mm × 155mm in length and width, with a transmittance of T 400～700 = 92%, GG3 high aluminosilicate glass with a pencil hardness of 9H, PMMA / PC composite plastic MB6001UR with a pencil hardness of 3H, and 20mm×20mm silicon wafer samples were ultrasonically cleaned in deionized water for 15min, dried with N2, and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 3×10 -3 Pa.

[0246] (2) Deposition of protective coating: Turn on the sample stage turret, set the rotation speed to 4 revolutions per minute, adjust the distance from the sample stage to the target surface to 10 cm, use a pulsed DC power supply to energize the Si target, introduce Ar and N2 gas, set the N2 gas flow rate to 300 sccm, set the gas volume to maintain the Ar to N2 gas ratio of 0.67:1, maintain the furnace pressure at 0.36 Pa, and set the power density of the Si target to 2.4 W / cm 2 , the pulse duty cycle is set to 60%, and the Si-N protective coating is deposited. By controlling the film formation time, the obtained film thickness is 520nm.

[0247] The coating prepared by the above method is Si 0.35 N 0.65 FTIR test of silicon wafer shows that its FTIR peak is 850cm -1 , the corresponding half-wave peak width is 363cm -1 , at 3230~3430cm -1 2040~2240cm -1 1450~1650cm -1 1050~1250cm -1 There is no absorption peak related to hydrogen, indicating that the coating does not contain hydrogen.

[0248] The protective coating prepared in Comparative Example 4 has a refractive index of 1.97 at 550 nm, a nanohardness value of 18 GPa for the film layer on the GG3 high alumina silicate glass substrate, and a Mohs hardness grade of 3 for the film layer on the GG3 high alumina silicate glass substrate.

[0249] The film layer on the GG3 high alumina silicate glass substrate was subjected to a steel wool test and failed the test (200 test results NG).

[0250] A 100-grid test was performed on the film layer on the GG3 high-alumina-silica glass substrate. Small debris was found at the intersection of the cutting lines, and the peeling area was less than 5% of the total area, reaching the Level 1 judgment level in GB / T 9286-2021. The test failed.

[0251] Durability tests were conducted on the film layer on the GG3 high-alumina-silica glass substrate and the film layer on the PMMA / PC composite board plastic. After 72 hours of high-temperature and high-humidity storage test, 72 hours of temperature shock test, and 48 hours of salt spray test, the coating showed a certain degree of shedding and failed the test.

[0252] Comparative Example 5

[0253] Comparative Example 5 provides a coating and a preparation method thereof, wherein the chemical composition of the coating is Si 0.55 N 0.45 , and its preparation method comprises the following steps:

[0254] (1) Pre-treatment: 71mm × 155mm in length and width, with a transmittance of T 400～700 = 92%, GG3 high aluminosilicate glass with a pencil hardness of 9H, PMMA / PC composite plastic MB6001UR with a pencil hardness of 3H, and 20mm×20mm silicon wafer samples were ultrasonically cleaned in deionized water for 15min, dried with N2, and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 3×10 -3 Pa.

[0255] (2) Deposition of protective coating: Turn on the sample stage turret, set the rotation speed to 4 revolutions per minute, adjust the distance from the sample stage to the target surface to 10 cm, use a pulsed DC power supply to energize the Si target, introduce Ar and N2 gas, set the N2 gas flow rate to 24 sccm, set the gas volume to maintain the Ar to N2 gas ratio of 1.5:1, maintain the pressure in the furnace at 0.06 Pa, and set the power density of the Si target to 2.4 W / cm 2 , the pulse duty cycle is set to 60%, and the Si-N protective coating is deposited. By controlling the film formation time, the obtained film thickness is 553nm.

[0256] The coating prepared by the above method is Si 0.55 N 0.45 FTIR test of silicon wafers showed that the FTIR peak position exceeded 838-875cm -1 range, and the corresponding FTIR half-wave peak width exceeds 247-313 cm -1 scope.

[0257] The protective coating prepared in Comparative Example 5 has a refractive index at 550 nm greater than 2.2, a nanohardness value of 20 GPa for the film layer on the GG3 high alumina silicate glass substrate, and a Mohs hardness grade of 4 for the film layer on the GG3 high alumina silicate glass substrate.

[0258] The film layer on the GG3 high alumina silicate glass substrate was subjected to a steel wool test and failed the test (200 test results NG).

[0259] A 100-grid test was performed on the film layer on the GG3 high-alumina-silica glass substrate. Small debris was found at the intersection of the cutting lines, and the peeling area was less than 5% of the total area, reaching the Level 1 judgment level in GB / T 9286-2021. The test failed.

[0260] Durability tests were conducted on the film layer on the GG3 high-alumina-silica glass substrate and the film layer on the PMMA / PC composite board plastic. After 72 hours of high-temperature and high-humidity storage test, 72 hours of temperature shock test, and 48 hours of salt spray test, the coating showed a certain degree of shedding and failed the test.

[0261] Comparative Example 6

[0262] Comparative Example 6 provides a coating and a preparation method thereof, wherein the chemical composition of the coating is Si 0.36 N 0.64 , and its preparation method comprises the following steps:

[0263] (1) Pre-treatment: 71mm × 155mm in length and width, with a transmittance of T 400～700 = 92%, GG3 high aluminosilicate glass with a pencil hardness of 9H, PMMA / PC composite plastic MB6001UR with a pencil hardness of 3H, and 20mm×20mm silicon wafer samples were ultrasonically cleaned in deionized water for 15min, dried with N2, and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 3×10 -3 Pa.

[0264] (2) Deposition of protective coating: Turn on the sample stage turret, set the rotation speed to 4 revolutions per minute, adjust the distance from the sample stage to the target surface to 10 cm, use a pulsed DC power supply to energize the Si target, introduce Ar-H2 mixed gas and N2 gas, set the N2 gas flow rate to 300 sccm, set the gas volume to maintain the Ar to N2 gas ratio of 0.60:1, the H2 to N2 gas ratio of 0.07:1, maintain the pressure in the furnace at 0.36 Pa, and set the power density of the Si target to 2.4 W / cm 2 , the pulse duty cycle was set to 60%, and the Si-NH protective coating was deposited. By controlling the film formation time, the obtained film thickness was 250 nm.

[0265] The coating prepared by the above method is Si 0.36 N 0.64 FTIR test was performed on the silicon wafer. As shown in Figure 5, the FTIR spectrum at 1167 cm -1 The peak at 3306 cm corresponds to the bending vibration of the NH bond. -1 The peak at corresponds to the stretching vibration of NH, indicating that the coating contains hydrogen, and the hydrogen content is greater than 1% in terms of atomic number. The main absorption peak of the Si-N bond in its FTIR spectrum is at 853 cm -1 , half-wave peak width is 232cm -1 .

[0266] The protective coating prepared in Comparative Example 6 has a refractive index of 1.91 at 550 nm, a nanohardness value of 18 GPa for the film layer on the GG3 high alumina silicate glass substrate, and a Mohs hardness grade of 3 for the film layer on the GG3 high alumina silicate glass substrate.

[0267] The film layer on the GG3 high alumina silicate glass substrate was subjected to a steel wool test and failed the test (200 test results NG).

[0268] A 100-grid test was performed on the film layer on the GG3 high-alumina-silica glass substrate. Small debris was found at the intersection of the cutting lines, and the peeling area was less than 5% of the total area, reaching the Level 1 judgment level in GB / T 9286-2021. The test failed.

[0269] Durability tests were conducted on the film layer on the GG3 high-alumina-silica glass substrate and the film layer on the PMMA / PC composite board plastic. After 72 hours of high-temperature and high-humidity storage test, 72 hours of temperature shock test, and 48 hours of salt spray test, the coating showed a certain degree of shedding and failed the test.

[0270] Comparative Example 7

[0271] Comparative Example 7 provides a coating and a preparation method thereof, wherein the chemical composition of the coating is Si 0.36 N 0.64 , and its preparation method comprises the following steps:

[0272] (1) Pre-treatment: 71mm × 155mm in length and width, with a transmittance of T 400～700 = 92%, GG3 high aluminosilicate glass with a pencil hardness of 9H, PMMA / PC composite plastic MB6001UR with a pencil hardness of 3H, and 20mm×20mm silicon wafer samples were ultrasonically cleaned in deionized water for 15min, dried with N2, and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 3×10 -3 Pa.

[0273] (2) Deposition of protective coating: Turn on the sample stage turret, set the rotation speed to 4 revolutions per minute, adjust the distance from the sample stage to the target surface to 10 cm, use a pulsed DC power supply to energize the Si target, introduce Ar and N2 gas, set the N2 gas flow rate to 280 sccm, set the gas volume to maintain the Ar to N2 gas ratio of 0.67:1, maintain the furnace pressure at 0.36 Pa, and set the power density of the Si target to 2.4 W / cm 2 The pulse duty cycle was set to 60% to deposit a Si-N protective coating. By controlling the film formation time, the resulting film thickness was 240nm. Ar and C2H2 gases were then introduced, with the C2H2 flow rate set to 400sccm. The gas volume was set to maintain a 1:1 Ar to C2H2 ratio, the furnace pressure was maintained at 0.8Pa, and the bias duty cycle was set to 75%. A DLC coating was deposited. By controlling the film formation time, the resulting film thickness was 20nm. Finally, a 20nm anti-fingerprint hydrophobic AF coating was deposited using a resistive evaporation source by controlling the film formation time.

[0274] In the protective coating prepared by the above method, the Si-N layer composition is Si 0.36 N 0.64The water contact angle of the film layer on the GG3 high alumina silicate glass substrate was tested to be 115°, the nano hardness value of the film layer on the GG3 high alumina silicate glass substrate was tested to be 19 GPa, the friction coefficient was 0.18, and the Mohs hardness grade of the composite film layer on the GG3 high alumina silicate glass substrate was tested to be 8.

[0275] The film layer on the GG3 high-alumina-silica glass substrate was subjected to a steel wool test and failed the test (3000 test results NG).

[0276] A 100-grid test was performed on the film layer on the GG3 high-alumina-silica glass substrate. Small debris was found at the intersection of the cutting lines, and the peeling area was less than 5% of the total area, reaching the Level 1 judgment level in GB / T 9286-2021. The test failed.

[0277] Durability tests were conducted on the film layer on the GG3 high-alumina-silica glass substrate and the film layer on the PMMA / PC composite board plastic. After 72 hours of high-temperature and high-humidity storage test, 72 hours of temperature shock test, and 48 hours of salt spray test, the coating showed a certain degree of shedding and failed the test.

[0278] Comparative Example 8

[0279] Comparative Example 8 provides a coating and a preparation method thereof, wherein the chemical composition of the coating is Si 0.44 N 0.56 , and its preparation method comprises the following steps:

[0280] (1) Pre-treatment: 71mm × 155mm in length and width, with a transmittance of T 400～700 = 92%, GG3 high aluminosilicate glass with a pencil hardness of 9H, PMMA / PC composite plastic MB6001UR with a pencil hardness of 3H, and 20mm×20mm silicon wafer samples were ultrasonically cleaned in deionized water for 15min, dried with N2, and placed in the vacuum chamber of the coating machine. The vacuum chamber was evacuated to 3×10 -3 Pa.

[0281] (2) Deposition of protective coating: Turn on the sample stage turret, set the rotation speed to 4 revolutions per minute, adjust the distance from the sample stage to the target surface to 10 cm, use a pulsed DC power supply to energize the Si target, introduce Ar and N2 gas, set the N2 gas flow rate to 240 sccm, set the gas volume to maintain the Ar to N2 gas ratio of 0.67:1, maintain the pressure in the furnace at 0.34 Pa, and set the power density of the Si target to 2.4 W / cm 2The pulse duty cycle was set to 60% to deposit a Si-N protective coating. By controlling the film formation time, the resulting film thickness was 731nm. Ar and C2H2 gases were then introduced, with the C2H2 flow rate set to 400sccm. The gas volume was set to maintain a 1:1 Ar to C2H2 ratio, the furnace pressure was maintained at 0.8Pa, and the bias duty cycle was set to 75%. A DLC coating was deposited. By controlling the film formation time, the resulting film thickness was 20nm. Finally, a 20nm anti-fingerprint hydrophobic AF coating was deposited using a resistive evaporation source by controlling the film formation time.

[0282] In the protective coating prepared by the above method, the Si-N layer composition is Si 0.44 N 0.56 The water contact angle of the film layer on the GG3 high alumina silicate glass substrate was tested to be 116°, the nano hardness value of the film layer on the GG3 high alumina silicate glass substrate was tested to be 18 GPa, the friction coefficient was 0.19, and the Mohs hardness grade of the composite film layer on the GG3 high alumina silicate glass substrate was tested to be 8.

[0283] The film layer on the GG3 high-alumina-silica glass substrate was subjected to a steel wool test and failed the test (3000 test results NG).

[0284] A 100-grid test was performed on the film layer on the GG3 high-alumina-silica glass substrate. Small debris was found at the intersection of the cutting lines, and the peeling area was less than 5% of the total area, reaching the Level 1 judgment level in GB / T 9286-2021. The test failed.

[0285] The durability tests of the film layer on the GG3 high-alumina-silica glass substrate and the film layer on the PMMA / PC composite board plastic were carried out, and the films were able to pass the 72h high-temperature and high-humidity storage test, the 72h temperature shock test, and the 48h salt spray test.

[0286] Comparative Example 9

[0287] Comparative Example 9: A Si-N coating was prepared by the method described in the reference paper Properties of Magnetron-Sputtered Silicon Nitride Films, T. Serikawa, et.al, J. Electrochem. Soc., 131(12): 2928-2933. Specifically, reactive magnetron sputtering was used with a sputtering power of 3 kW, a substrate temperature of 200°C, a sputtering gas flow rate of 100 sccm, a nitrogen partial pressure of 0.28 Pa, and a total sputtering pressure of 0.56 Pa to obtain a coating with a N / Si atomic ratio of 1.42 (Si 0.41 N 0.59 ), by analyzing the coating, the FTIR peak position is 840cm -1 , the corresponding half-wave peak width is 370cm-1 The half-wave peak width is large, indicating that the stress of the coating is large and it is easy to break. The refractive index is 1.97.

[0288] In the multifunctional protective coating of the present application, for the single-layer SiN coating, the Si x N y The coating (x, y is the atomic ratio), x and y satisfy: 0.39≤x≤0.43, 0.57≤y≤0.61, compared with comparative examples 1 to 4, it not only has a higher refractive index of 2.04 to 2.13 @ 550nm, a higher nanohardness of 25 to 30GPa, and a higher Mohs scratch hardness, but also has a peak position range of 838 to 875cm -1 It has a narrow half-wave peak width of 247 to 313 cm -1 , which means that the coating is not only dense and hard, but also has low stress. Using this SiN coating for a multi-layer coating structure not only makes the overall coating have a higher nanohardness, but also has a lower friction coefficient, thereby achieving high scratch resistance of the multi-layer coating. In Comparative Examples 1 to 4, the SiN coating composition is not within the scope defined in this application, and its refractive index is only 1.96 to 1.97@550nm, with a lower nanohardness of 19 to 21GPa and a lower Mohs scratch hardness, which may be related to the excessive Si-rich or N content in its coating, the insufficiently dense coating structure, and the high stress in the coating. For the multi-layer coating structure, compared with Comparative Examples 7 to 8, Examples 7 to 9 have higher nanohardness.

[0289] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some or all of the technical features therein. These modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application. Industrial Applicability

[0290] The multifunctional protective coating of the present application combines high refractive index, high nanohardness, high scratch resistance, low stress, and high durability. The multifunctional protective coating of the present application can be used as a protective coating for coated products. It can be used alone as a protective coating for coated products, or it can be used in combination with other coatings to impart high refractive index, high nanohardness, high scratch resistance, low stress, and high durability to the coated products.

Claims

1. Multifunctional protective coating, characterized in that: Contains chemical formula Si x N y The material meets the following characteristics: (a) x and y are atomic ratios, and 0.39≤x≤0.43, 0.57≤y≤0.61; (b) Fourier transform infrared spectrum with peak position in the range of 838-875 cm -1 The half-wave peak width at is 247 to 313 cm -1 ; (c) The refractive index at 550 nm is 2.0 to 2.2; (d) The hydrogen content is ≤ 1% by atomic number.

2. The multifunctional protective coating according to claim 1, characterized in that: The 550nm refractive index is 2.04-2.

13.

3. The multifunctional protective coating according to claim 1, characterized in that: Having at least one of the following characteristics: (1) The nanohardness of the coating is in the range of 25 to 30 GPa; (2) The thickness of the coating is 0.01 to 6.0 μm.

4. The method for preparing the multifunctional protective coating according to any one of claims 1 to 3, characterized in that: The steps include: The constituent elements of the multifunctional protective coating are deposited on at least a portion of the surface of the substrate in a preset proportion by physical vapor deposition to form the multifunctional protective coating.

5. The method for preparing the multifunctional protective coating according to claim 4, characterized in that: The multifunctional protective coating is formed by sputtering and depositing on at least a portion of the surface of the substrate using a silicon target under the condition of introducing a mixed gas of argon gas and nitrogen-containing gas.

6. The method for preparing the multifunctional protective coating according to claim 5, characterized in that: The nitrogen-containing gas is nitrogen, and the gas volume ratio of the argon gas to the nitrogen gas is (0.61-0.71):

1.

7. The method for preparing the multifunctional protective coating according to claim 6, characterized in that: The preparation method includes at least one of the following features: The temperature of sputtering deposition is 30-330°C; The total gas pressure of the mixed gas is 0.05-1.2 Pa; The nitrogen gas has a gas flow rate of 56 to 300 sccm; The power density of the silicon target is 1.5 to 2.4 W / cm 2 ; The bias voltage of the substrate is -180 to -20 V; The sputtering deposition time is 10 to 300 minutes; The background vacuum degree of the vacuum chamber used for sputtering deposition is ≤3.0×10 -3 Pa.

8. Use of the multifunctional protective coating according to any one of claims 1 to 3 or the multifunctional protective coating prepared by the preparation method of any one of claims 4 to 7 in coating products.

9. The use according to claim 8, characterized in that: The multifunctional protective coating serves as at least a part of the protective coating of the coated article.

10. A coated product, characterized in that: It comprises a substrate, and the multifunctional protective coating according to any one of claims 1 to 3 or the multifunctional protective coating according to any one of claims 4 to 7; The multifunctional protective coating is located on at least one side of the substrate.

11. The coated product according to claim 10, characterized in that: The surface material of the substrate is at least one of glass, plastic and silicon wafer.

12. The coated product according to claim 10, characterized in that: The coated product further comprises a diamond-like carbon film coating and / or an anti-fingerprint coating.